Nucleation layer for growth of iii-nitride structures

ABSTRACT

Nucleation layers for growth of III-nitride structures, and methods for growing the nucleation layers, are described herein. A semiconductor can include a silicon substrate and a nucleation layer over the silicon substrate. The nucleation layer can include silicon and deep-level dopants. The semiconductor can include a III-nitride layer formed over the nucleation layer. At least one of the silicon substrate and the nucleation layer can include ionized contaminants. In addition, a concentration of the deep-level dopants is at least as high as a concentration of the ionized contaminants.

BACKGROUND

High electron mobility transistors (HEMT's) grown on high resistivitysilicon (Si) can have degraded performance due to contamination duringfabrication. When a III-nitride layer is grown on a high resistivity Sisubstrate for use in a HEMT structure, acceptor contaminant species candeposit on and/or diffuse to the top surface of the Si substrate,causing a p-type region to form there upon ionization of the acceptors.The p-type region can have a high free hole concentration, resulting ina parasitic conductive channel. The parasitic channel results inparasitic capacitance that reduces the transistor performance at highfrequencies.

In addition, the surface of the Si substrate can be contaminated withoxygen, carbon, and other elements. The contaminants and impurities mayinclude species deposited on the surface of the substrate afterdesorbing from the chamber walls, adventitious carbon-containing speciesarising from species present in the environment, and/or a native oxideresulting from oxidation of the substrate by oxygen present in theambient environment. These contaminants and impurities can lead to theformation of a highly defective interface between the Si and theIII-nitride layer. This surface contamination and related defects canreduce the quality of the subsequent III-nitride epitaxial layers andstructures. This reduced quality causes reduced electron mobility,deteriorating transistor performance, especially at high-voltage andhigh-current conditions.

SUMMARY

Accordingly, nucleation layers for growth of III-V and III-nitridestructures, and methods for growing the nucleation layers, are describedherein. A semiconductor can include a substrate and a nucleation layerover the substrate. The nucleation layer can include deep-level dopants.The semiconductor can include a III-V layer formed over the nucleationlayer. At least one of the substrate and the nucleation layer caninclude ionized contaminants. In addition, a concentration of thedeep-level dopants is at least as high as a concentration of the ionizedcontaminants.

The substrate can include a substrate material, and the deep-leveldopants can include a deep-level dopant species having deep-level statesthat are separated from the conduction and valence bands of thesubstrate material by between 0.3 eV and 0.6 eV. The semiconductor caninclude a heterostructure between the substrate and the nucleationlayer.

The deep-level dopant can include one or more of vanadium, iron, sulfur,and other chemical elements. The ionized contaminants can include aGroup III species. The ionized contaminants can include ionized acceptorcontaminants.

The concentration of the deep-level dopants can be between 10¹⁵ cm⁻³ and10¹⁹ cm⁻³, and/or between 10¹⁶ cm⁻³ and 10¹⁸ cm⁻³. A concentration offree holes in the substrate and in the nucleation layer can be less than10¹⁶ cm⁻³ and/or less than 10¹⁵ cm⁻³.

A thickness of the nucleation layer can be between 1 nm and 100 nm,between 10 nm and 1 μm, and/or between 100 nm and 10 μm.

A first concentration of the deep-level dopants at the surface of thenucleation layer nearest the substrate can be higher than a secondconcentration of the deep-level dopants at the surface nearest the III-Vlayer. The substrate material can be silicon. The III-V layer can be aIII-nitride layer.

The nucleation layer and III-V layer can be grown by one or more ofmetalorganic chemical vapor deposition, molecular beam epitaxy, halidevapor phase epitaxy, and physical vapor deposition.

BRIEF DESCRIPTION OF THE DRAWINGS

The above and other features of the present disclosure, including itsnature and its various advantages, will be more apparent uponconsideration of the following detailed description, taken inconjunction with the accompanying drawings in which:

FIG. 1 depicts initial growth of a compensated nucleation layer usingmetalorganic chemical vapor deposition (MOCVD), according to anillustrative implementation;

FIG. 2 depicts the formation of an epitaxial nucleation layer at a timeafter the initial nucleation depicted in FIG. 1, according to anillustrative implementation;

FIG. 3 depicts the formation of a III-nitride layer on a substrate at atime after the time depicted in FIG. 2, according to an illustrativeimplementation;

FIG. 4 depicts a semiconductor manufactured using the methods describedherein, according to an illustrative implementation;

FIG. 5 depicts a semiconductor with III-nitride layers that can be usedto manufacture a high electron mobility transistor (HEMT), according toan illustrative implementation;

FIG. 6 depicts a HEMT manufactured using the methods described herein,according to an illustrative implementation; and

FIG. 7 depicts a flowchart of a method for growing semiconductors withnucleation layers that contain compensating deep-level dopants,according to an illustrative implementation.

DETAILED DESCRIPTION

The systems, devices, and methods described herein include, among otherthings, semiconductors having a nucleation layer that may achieveimproved performance. Though not to be bound by theory or a proposedmechanism of action, it is noted for purposes of clarity and instructionthat the nucleation layer may mitigate problems caused by parasiticchannels and contamination in at least two ways. First, doping thenucleation layer with deep-level dopant species may compensate for freeholes generated by the ionized acceptor dopants. Second, growth of thenucleation layer may clean the substrate surface, and the nucleationlayer can physically bury contaminants and impurities and relateddefects, such as dislocations. The semiconductor can includesemiconducting, conducting, and insulating materials. The semiconductormay include wafers covered with one or more blanket layers, wafers withone or more patterned layers, wafers with metal interconnects, waferswith functioning transistors, wafers with integrated circuits, one ormore separated portions of wafers such as a die or multiple dice, anddie or dice that have been packaged.

Although the systems, devices and methods described herein are notlimited to any particular mechanism of action, it is noted for purposesof clarity that the deep-level dopants may act as deep-level traps andmay compensate for the ionized acceptor dopants that deposit on ordiffuse to the substrate surface. As deep-level traps, the deep-leveldopants provide recombination centers, and trap and localize free holescaused by the ionized acceptor contaminants. The holes may be bound tothe deep-level dopants and are not delocalized (free) throughout thesubstrate or nucleation layer. This trapping is understood to lower thefree hole concentration near the surface of the substrate, making theregion more resistive.

It is also understood and noted for purposes of clarity, that thenucleation layer may physically bury contaminants and impurities thatdeposit on, or have reacted with the top surface of the substrate. Areducing atmosphere (typically comprising H₂ gas) occurring before andduring growth of the nucleation layer is understood to remove some orall of the carbon- and oxygen-containing contaminants and impurities,but the nucleation layer buries any contaminants and impurities thatremain. In addition, the nucleation layer can be thick enough so thatdislocations terminate within it and the upper surface of the nucleationlayer has a reduced dislocation density. By burying contaminants,impurities, and the dislocations they cause, it is understood that thenucleation layer provides a clean surface for growth of a subsequentIII-nitride layer. The III-nitride layer is a layer comprising a GroupIII species and nitrogen. The Group III species can include one or moreelement in Group III of the Periodic Table, including B, Al, Ga, In, andTl. The III-nitride layer can be a compound that includes multiple GroupIII elements. The III-nitride layer can include binary compounds such asGaN, ternary compounds such as Al_(x)Ga_(1-x)N (0≦x≦1) andIn_(x)Ga_(1-x)N (0≦x≦1), quaternary compounds such asIn_(x)Al_(y)Ga_(1-x-y)N (0≦x,y≦1), and quinary compounds such asGa_(x)In_((1-x))As_(y)Sb_(z)N_((1-y-z)) (0≦x,y,z≦1). The III-nitridelayer can be undoped, unintentionally doped, or doped with donor oracceptor dopants. Throughout this disclosure, a III-nitride layer isdescribed in detail as an example of a III-V layer. However, III-nitridematerials are but a subset of III-V materials, and layers and materialsdescribed herein as III-nitride layers and materials can be replacedwith other III-V layers and materials. III-V layers and materialsinclude one or more species from Group III of the Periodic Table (suchas the examples listed above) and one or more species from Group V ofthe Periodic Table (such as N, P, As, Sb, and Bi). As later describedwith reference to FIG. 4, examples of other III-V materials include oneor more of GaAs, InP, InAs, InSb, InGaAs, GaAsP, InGaAsP, and the like.

FIG. 1 depicts initial growth of a compensated nucleation layer usingmetalorganic chemical vapor deposition (MOCVD). FIG. 1 depicts asubstrate 102, a chamber wall 104, a residue layer 114 on the chamberwall 104, and a precursor inlet 106. The substrate 102 can be anysubstrate used for growth of III-nitride materials. The substrate 102can be a silicon substrate, a high-resistivity silicon substrate, asilicon-on-insulator (SOI) substrate, and/or any type of compositesubstrate in which the top surface comprises silicon. The abovesubstrates and other substrates can include single-crystal wafers thatare undoped, unintentionally doped, or doped with donor or acceptordopants. In the example of a high-resistivity silicon substrate, thesubstrate can have a resistivity of greater than 1,000 ohm-cm, greaterthan 2,000 ohm-cm, greater than 3,000 ohm-cm, greater than 6,000 ohm-cm,or greater than 10,000 ohm-cm. The substrate 102 can be a silicon (111)substrate to facilitate epitaxial growth of III-nitride materials, orthe substrate 102 can include silicon with another crystal orientationsuch as silicon (100).

The precursor inlet 106 schematically represents a precursor deliverysystem, which injects the various precursors required to deposit siliconand III-nitride layers on the substrate 102. As depicted in FIG. 1, theprecursor injector 106 is injecting a gas-phase silicon precursor 120and a gas-phase dopant precursor 121.

Elevating the temperature of the chamber wall 104 is understood to causecomponents of the residue layer 114 to desorb as gas-phase contaminantspecies 116. The residue layer 114 can be a III-nitride material thatwas deposited on the chamber wall 104 during previous operation of thedeposition system. Thus, the contaminant species 116 can be a Group IIIspecies which would act as a p-type dopant in silicon. A portion of thegas-phase species 120, 121, and 116 deposit on the substrate 102 assurface species 124, 125, and 118, respectively. The surface species124, 125, and 118 can be physisorbed or chemisorbed, and can be crackedor uncracked. The silicon surface species 124 is the dominant species onthe surface of the substrate 102, but the dopant surface species 125 andthe contaminant surface species 118 are present in concentrations highenough to affect the doping level of the film that is subsequently grownon the substrate 102. In some examples, the flow of the gas-phaseprecursor species 121 from the precursor injector 106 is adjusted suchthat the concentration of the dopant species 125 on the substrate 102 issubstantially the same as the concentration of the contaminant species118 on the substrate 102. If diffusion from subsequently depositedlayers is expected, the flow of the gas-phase precursor species 121 canbe adjusted to result in a concentration of the dopant species 121 thatis higher than the concentration of the contaminant species 118. Inaddition, some of the silicon precursor species 120 and the dopantspecies 121 deposit as surface species 122 and 123, respectively, on theresidue layer 114.

The silicon precursor species 120 can include one or more silicon CVDprecursors. Examples of silicon CVD precursors include silane, disilane,trisilane, dichlorosilane, trichlorosilane, methylsilane,diterttiarybutylsilane, silicon tetrachloride, silicon tetrafluoride,silicon tetrabromide, tetraethoxysilane, elemental silicon, andhigher-order silanes and chlorosilanes.

The dopant species 121 can include one or more CVD precursors thatdeliver deep-level dopants. Examples of deep-level dopants includesulfur, selenium, vanadium, iron, tantalum, tellurium, chromium,manganese, or other chemical elements. Examples of CVD precursors thatdeliver sulfur include hydrogen sulfide (H₂S), ditert-butyl sulphide,bis(trimethylsilyl)sulfide, (R)-(+)-t-butylsulfinamide, diethyl sulfide,polypropylene sulfide, diisopropylsulfide, elemental sulfur, andorganics, cyclopentadienyls, amines, aminidates, halides, and aromaticscontaining sulfur.

Examples of CVD precursors that deliver selenium include hydrogenselenide (H₂Se), dimethylselenide, ditert-butylselenide, elementalselenium, and other chemical compounds containing selenium.

Examples of CVD precursors that deliver vanadium includebis(cyclopentadienyl)vanadium(II), vanadium(V) oxytriisopropoxide,tetrakis(dimethylamino)vanadium(IV), tetrakis(diethylamino)vanadium(IV),elemental vanadium, and organometallics, and cyclopentadienyls, amines,aminidates, halides, and aromatics containing vanadium.

Examples of CVD precursors that deliver iron includebis(cyclopentadienyl)iron (also known as ferrocene), butylferrocene,dichlorophosphinoferrocene, ethylferrocene, elemental iron, andcyclopentadienyls, amines, aminidates, halides, elemental vanadium, andaromatics containing iron.

Examples of the contaminant species 118 include boron, aluminum,gallium, indium, thallium, and nitrogen.

FIG. 2 depicts the formation of an epitaxial nucleation layer 236 at atime after the initial nucleation depicted in FIG. 1. The surfacespecies 124, 125, and 118 depicted in FIG. 1 have coalesced into anucleation layer 236. The nucleation layer 236 is an epitaxial layerthat is lattice-matched to, or is at least pseudomorphic with, thesubstrate 102. The nucleation layer 236 can be a silicon layer. If thesubstrate 102 is a silicon substrate and/or includes silicon as asubstrate material, the nucleation layer 236 can be a homoepitaxialsilicon layer. Homoepitaxy refers to the epitaxial growth of a materialon a substrate having at least a top surface of the same material.However, a homoepitaxial layer can include different dopingcharacteristics (such as dopant species and concentration) than thematerial below. The nucleation layer 236 contains silicon 225,deep-level dopant species 227, and ionized acceptor contaminant species226, resulting from incorporation of the surface species 124, 125, and118, respectively. The ionized acceptor contaminant species 226 caninclude Group III species such as B, Al, Ga, In, and Tl. The deep-leveldopant species 227 can include one or more of S, Se, V, Fe, Ta, Te, Cr,Mn, and other chemical elements. The deep-level dopant species 227 andthe ionized acceptor contaminant species 226 can be interstitial orsubstitutional impurities. In some examples, one or both of the species226 and 227 are interstitial impurities as deposited and becomesubstitutional impurities after annealing. The annealing can occur inthe deposition chamber or in a separate chamber.

When using a high-resistivity silicon wafer as the substrate 102, thepresence of p-type dopants as the contaminant species 118 could lead top-type doping of the substrate 102. The free holes resulting from thisp-type doping could lead to the formation of a low-resistivity (highmobility) parasitic channel in the substrate 102. However, supplying adeep-level dopant that contains deep-level donor states as the dopantspecies 121 results in the deep-level dopant species 227 trapping thefree holes, thus compensating for the p-type doping. When theconcentration of the deep-level dopant species 227 is at least as highas the concentration of the ionized acceptor contaminant species 226,the deep-level dopant species 227 compensates for the free holesgenerated by the ionized acceptor contaminant species 226, preventingthe formation of a parasitic channel and maintaining the highresistivity of the substrate 102.

As described herein, the electrical activity of both deep-level dopantsand acceptor contaminants is approximately 1. The electrical activity ofa species refers to the fraction of atoms of that species that areionized. Thus, nearly all of the acceptors and deep-level dopants areionized and the concentration of ionized acceptors or deep-level dopantsis approximately equivalent to the concentration of acceptor contaminantspecies or deep-level dopants. However, in some examples, the electricalactivity of the deep-level dopants and/or the acceptors is less than 1.In these examples, the concentration of ionized deep-level dopants is atleast as high as the concentration of ionized acceptors. Concentrationsof dopants and charge carriers are sometimes expressed in units ofelectrons-cm⁻³, holes-cm⁻³, or atoms-cm⁻³, but more often, the name ofthe particle is omitted while referencing the same quantity and suchconcentrations are simply expressed in units of cm⁻³. A concentration ofdeep-level dopant species that is at least as large as a concentrationof ionized acceptor contaminant species can include a concentration ofdeep-level dopant species that is more than 10% lower than,approximately 10% lower than, approximately 5% lower than, approximatelyequal to, approximately 5% greater than, approximately 10% greater than,or more than 10% greater than the concentration of ionized acceptorcontaminant species.

If the concentration of ionized acceptor contaminant species is largerthan the concentration of deep-level dopant species, the free holeconcentration in the nucleation layer and the nearby portion of thesubstrate will be the difference between the concentration of ionizedacceptor contaminant species and the concentration of deep-level dopantspecies. Thus, a concentration of deep-level dopant species that is 10%lower than the concentration of ionized acceptor contaminant specieswill result in a reduction in free hole concentration of an order ofmagnitude, compared to a semiconductor without deep-level dopants.

If the concentration of deep-level dopant species is exactly equal tothe concentration of ionized acceptor contaminant species, a fullycompensated condition exists and the free hole and electronconcentrations in the nucleation layer and the nearby portion of thesubstrate will be negligible, due only to thermally generated carriers.

If the concentration of deep-level dopant species is larger than theconcentration of ionized acceptor contaminant species, a fullycompensated condition also exists and the free hole and electronconcentration in the nucleation layer and the nearby portion of thesubstrate will also be negligible, due only to thermally generatedcarriers. The concentrations of thermally generated carriers in fullycompensated conditions are negligible because the deep-level dopantspecies do not have any electron energy states within several multiplesof kT (up to 0.3-0.6 eV) from either the conduction or valence bands ofsilicon. Here, k refers to Boltzmann's constant and T refers to thetemperature of the semiconductor in Kelvins.

At the time depicted in FIG. 2, the surface species 122 and 123 havecoalesced into a residue layer 228 that covers the residue layer 114.The residue layer 228 includes silicon material 229 and dopant species233.

The gas-phase precursor species 120 and 121 continue to travel to thesubstrate 102 and deposit as surface species 224 and 225, respectively.In addition, the gas-phase species 120 and 121 travel to the wall 104and deposit on the residue layer 228 as surface species 222 and 223,respectively.

The residue layer 228 is at an elevated temperature due to the growthconditions and thus some of its component species desorb as siliconspecies 230 and dopant species 231. The desorbed species 230 and 231 canalso travel to the substrate 102 and deposit as surface species.However, because the residue layer 228 covers the residue layer 114,contaminant species such as the contaminant species 116 do not desorb.Thus, once the residue layer 228 has formed, it prevents further p-typedopants, such as Group III elements, from depositing on the substrate102. Furthermore, because the concentration of deep-level dopant species227 is at least as high as the concentration of ionized acceptorcontaminant species 226, the substrate 102 does not contain a parasiticchannel.

FIG. 3 depicts the formation of a III-nitride layer on the substrate 102at a time after the time depicted in FIG. 2. In FIG. 3, the precursorinjection system 106 delivers III-nitride precursors 340. TheIII-nitride precursors 340 can include multiple species of precursor andcan be injected by different precursor delivery lines. The III-nitrideprecursors can include precursors that deliver Group III elements suchas boron, aluminum, gallium, indium, and thallium, and/or nitrogen.

Examples of precursors that deliver aluminum include trimethylaluminum,triethylaluminum, dimethylaluminumhydride, dimethylethylamine alane,triisobutylaluminum, tris(dimethylamido)aluminum(III), aluminumtrichloride, elemental aluminum, and alkyls, alkylamides, alkoxides,amidinates, β-diketonates, carbonyls, cyclopentadienyls, andorganometallics containing aluminum.

Examples of precursors that deliver gallium include trimethylgallium,triethylgallium, tris(dimethylamido)gallium(III), gallium trichloride,diethylgallium chloride, triisobutylgallium, elemental gallium, andalkyls, alkylamides, alkoxides, amidinates, β-diketonates, carbonyls,cyclopentadienyls, and organometallics containing gallium.

Examples of precursors that deliver indium include trimethylindium,triethylindium, dimethylethylindium, indium trichloride, elementalindium, and alkyls, alkylamides, alkoxides, amidinates, β-diketonates,carbonyls, cyclopentadienyls, and organometallics containing indium.

Examples of precursors that deliver nitrogen include ammonia,1.1-dimethylhydrazine, tert-butylamine, phenylhydrazine, elementalnitrogen, and other gases and organometallics containing nitrogen.

The III-nitride precursors travel to the substrate 102 and deposit assurface species 342. The precursor species 340 also travels to the wall104 and deposits as surface species 343. As the deposition progresses,the surface species 343 form a III-nitride layer 341 over the residuelayer 228. Likewise, the surface species 342 form a III-nitride layer348 over the silicon layer 236 on the substrate 102. The III-nitridelayer 346 can include one or more Group III elements.

Because of the elevated temperature of the wall 104, III-nitride species345 will desorb from the III-nitride layer 341. The III-nitride species345 can then deposit on to the substrate 102 as surface species 342.However, once the III-nitride layer 341 is continuous and dense, itprevents the sublimation of silicon species from the residue layer 228.Thus, desorption from a continuous and dense III-nitride layer 341 doesnot significantly affect the composition of the III-nitride layer 348.However, before the III-nitride layer 341 becomes continuous and dense,some species from the residue layer 228 can sublimate and can bedeposited in the lower portion of the III-nitride layer 348 as siliconspecies 346 and dopant species 347. When a subsequent wafer is loadedinto the chamber, the III-nitride layer 341 can act as a source ofcontaminant species in a similar manner for the subsequent wafer as theresidue layer 114 acts for the substrate 102.

In addition to ionized acceptor species that are deposited in thesilicon layer 236 due to desorption from the residue layer 114, thesilicon layer 236 can also include ionized acceptor contaminant species350 that diffuse down from the III-nitride layer 348. This diffusion canoccur at significant rates because the substrate 102 is at an elevatedtemperature during the deposition process. In particular, gallium andaluminum can diffuse into the silicon layer 236 and act as ionizedacceptor dopants, making the silicon layer 236 more p-type and moreconductive. However, the flux of the dopant species 121 during growth ofthe silicon layer 236 can be selected to produce a concentration ofdeep-level dopants in the silicon layer 236 that is sufficient tocompensate for both ionized acceptor contaminant species 226 originatingin the residue layer 114 and ionized acceptor contaminant species 350that have diffused from adjacent layers.

The deep-level dopant species 227 compensate for the p-type dopantspresent in the silicon layer 236 by acting as deep-level traps. Asdeep-level traps, the deep-level dopant species 227 providerecombination centers, which trap and localize free holes caused by theionized acceptor contaminant species 226 and 350. This trapping lowersthe free hole concentration in the silicon layer 236, making it moreresistive. In some examples, the ionized acceptor contaminant species226 are present in the silicon layer 236 at a concentration ofapproximately 10¹⁷ cm⁻³. The ionized acceptor contaminant species 226can be present at a concentration between 10¹⁵ and 10¹⁷ cm⁻³, between10¹⁴ and 10¹⁸ cm⁻³, and/or between 10¹¹ and 10²⁰ cm⁻³. To compensate forthe free holes generated by these p-type dopants, the silicon layer 236can contain at least an equivalent concentration of deep-level dopantspecies 227. Thus, in this example, the silicon layer 236 should containa concentration of deep-level dopant species 227 of at least 10¹⁷ cm⁻³,between 10¹⁵ and 10¹⁹ cm⁻³, between 10¹⁶ and 10¹⁸ cm⁻³, or higher than10¹⁸ cm⁻³. With the deep-level dopant species 227 compensating for thepresence of free holes, the free hole concentration can be less than10¹⁸ cm⁻³, less than 10¹⁷ cm⁻³, less than 10¹⁶ cm⁻³, and/or less than10¹⁵ cm⁻³. In some examples, the deep-level dopant species 227 can actas a recombination center, even though the original deep-level trapstates have been compensated by free holes. For example, the deep-leveldopant species in the silicon layer 236 can re-capture electrons fromthe conduction band, which then recombine with other free holes. It isalso possible that the deep-level dopant species 227 can directlycapture free holes.

To act as a deep-level trap, the deep-level dopant species 227 shouldhave an ionization energy that results in electron states well insidethe band gap of the silicon layer 236, far from the band edges. Thesedeep-level states should be separated from the conduction and valenceband edges by significantly more than the thermal energy of electrons(kT) at room temperature. For example, the deep-level states can beseparated from one or both of the band edges by between 0.3 and 0.5 eV.In some examples, the deep-level states can be separated from one orboth of the band edges by between 0.2 and 0.6 eV, and/or by more than0.6 eV. One or more of sulfur (S), vanadium (V), iron (Fe), selenium(Se), tantalum (Ta), tellurium (Te), chromium (Cr), manganese (Mn), andother chemical elements act as deep-level traps in silicon and can beused as the deep-level dopant species 227.

FIG. 4 depicts a semiconductor 400 manufactured using the methodsdescribed herein. The semiconductor 400 includes a substrate 402 (e.g.,102), a nucleation layer 436 (e.g., 236) over the substrate 402, and aIII-nitride layer 448 (e.g., 348) over the nucleation layer 436. In someexamples, the III-nitride layer 448 may be replaced with a III-V layer.Examples of III-V materials include one or more of GaAs, InP, InAs,InSb, InGaAs, GaAsP, InGaAsP, and the like. The substrate 402 can be asilicon substrate or a high-resistivity silicon substrate. In theexample of a high-resistivity silicon substrate, the substrate can havea resistivity of greater than 1,000 ohm-cm, greater than 2,000 ohm-cm,greater than 3,000 ohm-cm, greater than 6,000 ohm-cm, or greater than10,000 ohm-cm. The substrate 102 can be a silicon (111) substrate tofacilitate epitaxial growth of the III-nitride layer 448. The thicknessof the nucleation layer 436 can be approximately 1 μm, between 1 nm and10 μm (microns or micrometers), between 1 nm and 100 nm, between 10 nmand 1 μm, between 100 nm and 1 μm, and/or between 100 nm and 10 μm.

The nucleation layer 436 buries contaminants and impurities present onthe surface of the substrate 402. The contaminants and impurities mayinclude species deposited on the surface of the substrate afterdesorbing from the chamber walls, as illustrated by species 118 inFIG. 1. The contaminants and impurities may also include adventitiouscarbon-containing species arising from species present in theenvironment and/or a native oxide resulting from oxidation of thesubstrate 402 by oxygen present in the ambient environment. A reducingatmosphere (typically comprising H₂ gas) before and during growth of thenucleation layer 436 can remove some or all of the carbon- andoxygen-containing contaminants and impurities, but the nucleation layerburies any contaminants and impurities that remain. In some examples,the nucleation layer 436 is thick enough that dislocations and otherdefects terminate within it and the upper surface of the nucleationlayer 436 has a reduced defect density.

Furthermore, the nucleation layer 436 physically buries the contaminantsand impurities, providing a clean surface for growth of the III-nitridelayer 448. In some examples, the nucleation layer 436 does not containdeep-level dopants. In these examples, the nucleation layer 436 servesto provide a clean surface for growth of the III-nitride layer 448 butdoes not affect the carrier concentration by compensating for impuritiesthat may be present. By physically burying contaminants and impurities,the nucleation layer 436 improves the film quality of the III-nitridelayer 448, improving the performance of HEMT devices made using thesemiconductor 400. By compensating ionized acceptor contaminant species,the nucleation layer 436 reduces or eliminates the formation of aparasitic conductive channel, improving the performance of HEMT devicesmade using the semiconductor 400.

The III-nitride layer 448 can include one or more constituent layers.The semiconductor 400 can be an epi-wafer, that is, a semiconductorwafer covered with blanket epitaxial layers and no lateral patterning.The epi-wafer may include one or more non-epitaxial capping layers aswell. The epi-wafer can be further processed by lateral patterning tocreate transistors. In some examples, the semiconductor 400 is a waferthat has undergone such patterning. The semiconductor 400 can alsoinclude other layers (such as metal layers serving as contacts and/orinterconnects) over the III-nitride layer 448 as well. In some examples,the semiconductor 400 is a portion of an epi-wafer, such as a chip thathas been diced from an epi-wafer.

FIG. 5 depicts a semiconductor 500 with III-nitride layers that can beused to manufacture a high electron mobility transistor (HEMT). Thesemiconductor 500 includes a substrate 502 (e.g., 402, 102) and anucleation layer 536 (e.g., 436, 236) over the substrate 502. Thesemiconductor 500 also includes a III-nitride layer 548 (e.g., 348,448). The III-nitride layer 548 comprises multiple layers, including atransition layer 550, a buffer layer 552, a gallium nitride (GaN) layer554, and an indium aluminum gallium nitride (In_(x)Al_(y)Ga_(1-x-y)N; 0

x, y

1) layer 558. The In_(x)Al_(y)Ga_(1-x-y)N layer 558 can have a constantcomposition (i.e., constant values of x and y) through its thickness, orcan have a varying composition (i.e., varying values of x and y) throughits thickness. In some examples, the III-nitride layer can comprise oneor more layers that include materials other than III-nitrides. Thetransition layer 550 may contain AlN and/or other alloys such asIn_(x)Al_(y)Ga_(1-x-y)N, and can serve to transition between thenucleation layer 536, which can be made of silicon and the buffer layer552, which can comprise GaN. The buffer layer 552 can comprise arelatively thick GaN layer that is thick enough to be fully relaxed atits upper surface. The buffer layer 552 can also act to reduce a densityof the defects due to lattice mismatch. The buffer layer can compriseany III-nitride material, such as GaN, In_(x)Al_(y)Ga_(1-x-y)N, and/orAlN. In some examples, the composition of the buffer layer can varythroughout its thickness. The buffer layer can also comprise one or moresuperlattices or multiple layer structures with alternating layers ofIII-nitride materials.

Due to the heterojunction between the GaN layer 554 and theIn_(x)Al_(y)Ga_(1-x-y)N layer 558, a two-dimensional electron gas (2DEG) forms in the GaN layer 554 near the GaN/In_(x)Al_(y)Ga_(1-x-y)Ninterface. The 2 DEG 556 can provide a high-electron mobility channel ina HEMT. Other layers can be deposited over the semiconductor 500,including one or more of a capping layer, a metallization layer, and anisolation layer. Lateral patterning can be used to define lateralfeatures such as transistors in the semiconductor 500. The semiconductor500 can be an epi-wafer, and may include one or more non-epitaxialcapping layers. In some examples, the semiconductor 500 includes one ormore patterned features such as transistors. The semiconductor 500 canalso include other layers (such as metal layers serving as contactsand/or interconnects) over the III-nitride layer 548 as well. In someexamples, the semiconductor 500 is a portion of an epi-wafer, such as achip.

By physically burying contaminants and impurities, the nucleation layer536 improves the film quality of the III-nitride layer 548, improvingthe performance of HEMT devices made using the semiconductor 500. Bycompensating ionized acceptor contaminant species, the nucleation layer536 reduces or eliminates the formation of a parasitic conductivechannel, improving the performance of HEMT devices made using thesemiconductor 500.

FIG. 6 depicts a HEMT 600 manufactured using the methods describedherein. The HEMT 600 can be manufactured from the semiconductor 500. TheHEMT 600 includes a substrate 602 (e.g., 102, 402, 502) and a nucleationlayer 636 (e.g., 236, 436, 536). The HEMT 600 also includes aIII-nitride layer 648 (e.g., 348, 448, 548) over the nucleation layer636. The III-nitride layer 648 includes a transition layer 650 (e.g,550) over the nucleation layer 636, a buffer layer 652 (e.g., 552) overthe AN layer 650, a GaN layer 654 (e.g., 554) over the buffer layer 652,and an In_(x)Al_(y)Ga_(1-x-y)N (0

x, y

1) layer 658 (e.g., 558) over the GaN layer 654. TheIn_(x)Al_(y)Ga_(1-x-y)N layer 658 can have a constant composition (i.e.,constant values of x and y) through its thickness, or can have a varyingcomposition (i.e., varying values of x and y) through its thickness. TheHEMT 600 also includes a 2 DEG 656 (e.g., 556) in the gallium nitridelayer 654 near its interface with the In_(x)Al_(y)Ga_(1-x-y)N layer 658.The III-nitride layer 648 can have a composition different than isdepicted in FIG. 6. The III-nitride layer 648 in the HEMT 600 arelaterally patterned using photolithography and etching techniques.Metallic contacts are deposited on the III-nitride layers to form asource contact 660, a drain contact 662, and a gate contact 664.Interconnects (not shown) can connect the contacts 660, 662, and 664 toa circuit. A gate voltage applied to the gate contact 664 can modulatethe conductivity of the channel between the source contact 660 and thedrain contact 662.

Because the 2 DEG 656 provides a channel with high mobility, the HEMT600 can be used for high-frequency switching. The switching can be atfrequencies higher than 1 GHz, 50 GHz, or 60 GHz. At these highfrequencies, any parasitic capacitance of the substrate 602 can reducethe performance of the HEMT 600. However, the nucleation layer 636 ofthe HEMT 600 includes deep-level dopants (e.g., 227) that act as trapsand compensate for the presence of ionized acceptors, reducing orsubstantially preventing a parasitic channel and thus reducing orsubstantially preventing parasitic capacitance of the substrate 602.Accordingly, deep-level dopants (e.g., 227) in the nucleation layer 636can improve the performance of the HEMT 600 at high frequencies. Theincrease in performance can be realized as one or both of operating athigher frequencies and increased gain at a given frequency. Byphysically burying contaminants and impurities, the nucleation layer 636improves the film quality of the III-nitride layer 648, improving theperformance of HEMT devices made using the semiconductor 600.

FIG. 7 depicts a flowchart of a method 700 for growing semiconductorswith nucleation layers that contain compensating deep-level dopants. Themethod 700 can be an MOCVD process and/or an organometallic vapor phaseepitaxy (OMVPE) process. In some examples, the method 700 can beimplemented using molecular beam epitaxy (MBE), halide vapor phaseepitaxy (HVPE), pulsed laser deposition (PLD), and/or physical vapordeposition (PVD) instead of MOCVD. A substrate can be loaded directlyinto an epitaxial chamber or using a transfer (load-lock) chamber. At702, conditions in the epitaxial chamber or load-lock chamber areadjusted to wafer loading conditions. The substrate holder is cooled toroom temperature. A N₂ purge gas flow is adjusted to near 0. At 704, oneor more substrates (e.g., 102, 402, 502, 602) is loaded into theepitaxial chamber or loaded into the load-lock chamber and thentransferred into the epitaxial chamber. If the load-lock chamber isused, the epitaxial chamber remains under the base state conditions.

At 706, the epitaxial chamber conditions are adjusted to growthconditions for the nucleation layer (e.g., 236, 436, 536, 636). The oneor more substrates (e.g., 102, 402, 502, 602) is heated to a temperatureof 550-1200° C. The pressure in the epitaxial chamber is adjusted to40-760 Torr. A very low pressure technique (<50 Torr) can be alsoemployed. A purge gas flow of H₂, N₂, or a mixture of both, is adjustedto 1-1000 slm (standard liters per minute). In some examples, a carriergas is not used. The precursors flow rate for the nucleation layergrowth is controlled in the range of 1-500 μmol/min. Depending on thedesired growth rate, the precursors flow rate can be also adjusted inthe wide range of 0.1-5000 μmol/min.

At 708, the nucleation layer (e.g., 236, 436, 536, 636) is grown overthe one or more substrates. Step 708 is continued for a predeterminedtime, corresponding to a desired thickness of the nucleation layer. Thedesired thickness can be approximately 1 μm, between 1 nm and 10 μm,between 1 nm and 100 nm, between 10 nm and 1 μm, between 100 nm and 1μm, and/or between 100 nm and 10 μm. The nucleation layer includesdeep-level dopants (e.g., 227) to compensate for contaminant species(e.g., 118, 350) that are present due to chamber contamination and/ordiffusion. The flow rate of the deep-level dopant precursor (e.g., 121)is typically lower than the precursors flow rate for the mainconstituents of the nucleation layer and can be constant during thegrowth of the nucleation layer, or it can be adjusted during the growth.This flow rate can be reduced, even to zero, as the chamber walls becomecoated with silicon, blocking desorption of contaminant species fromresidue layers (e.g., 114) on the chamber walls. These conditionsproduce a concentration of deep-level dopants at the surface of thenucleation layer (e.g., 236, 436, 536, 636) nearest the one or moresubstrates (e.g., 102, 402, 502, 602) that is higher than theconcentration at the surface of the nucleation layer nearest theIII-nitride layer (e.g., 348, 448, 548, 648). Thus, the concentration ofdeep-level dopants is graded and tailored to be high in regions wherethe ionized acceptor concentration is high and low where the ionizedacceptor concentration is low.

In some examples, the method 700 does not include flowing deep-leveldopant precursors (e.g., 121) into the epitaxial chamber, and thenucleation layer (e.g, 236, 436, 536, 636) does not contain deep-leveldopants. In these examples, the nucleation layer serves to provide aclean surface for growth of the III-nitride layers (e.g., 348, 448, 548,648) but does not compensate for impurities present. The nucleationlayer can provide a clean surface by burying impurities and defectspresent on the surface of the one or more substrates (e.g., 102).

At 710, the epitaxial chamber conditions are adjusted to conditions forIII-nitride growth. The wafer (e.g., 102, 402, 605, 602) is heated to atemperature of about 550-1100° C. The pressure in the chamber isadjusted to 40-760 Torr. A very low pressure technique (<50 Torr) can bealso employed. A purge gas flow of H₂, N₂, or a mixture of both, isadjusted to 1-1000 slm. In some examples, no purge gas can be used. Thegroup III element precursors flow rate is controlled in the range of10-500 μmol/min. The group V element precursor flow rate is controlledin the range of 0.001-10 mol/min. At 712, III-nitride layers (e.g., 348,448, 548, 648) are grown over the nucleation layer. The III-nitridelayers can include multiple layers, and can include non-III-Vcomponents.

At 714, the epitaxial chamber conditions are adjusted for unloading theone or more substrates. If the load-lock chamber is used for thesubstrate loading, the epitaxial chamber conditions are adjusted to thebase state conditions. If the substrate unloading is carried outdirectly from the epitaxial chamber, the wafer (e.g., 102, 402, 605,602) is cooled to about room temperature, or at least below about 450°C. An N₂ purge gas flow is adjusted to near 0. At 716, the one or moresubstrates are unloaded from the growth chamber.

Although the above description discloses III-nitride layers over asubstrate that contains silicon, other material combinations arepossible. The substrate can be made of one or more materials other thansilicon. For example, the substrate can include one or more of sapphire,GaAs, GaN, InP, and other materials. The substrate can include aheterostructure between the nucleation layer and the III-nitride layer.The heterostructure may include multiple layers of different materials.

Examples of heterostructures include Si-on-insulator (SOI) andSi-on-sapphire (SOS) substrates. A nucleation layer could be grown overan SOI or an SOS substrate. The nucleation layer could be between theoxide layer and the Si layer, or above the Si layer, in an SOI or an SOSsubstrate. The Si layer of the SOI or SOS substrate could itself be thenucleation layer. The nucleation layer could be grown directly on thesapphire or handle wafer. A nucleation layer could be grownhomogeneously with a layer of the same material but involved in aprocess similar to a heterostructure growth process, such as anepitaxial layer transfer process. In such an epitaxial layer transferprocess, the epitaxial layer could comprise the nucleation layer. Thus,the epitaxial layer could include a first portion with deep-leveldopants and a second portion that is unintentionally doped, or all ofthe epitaxial layer could be doped with deep-level dopants of constantor varying concentration.

In general, the nucleation layer can compensate either acceptor or donorcontaminants by containing either deep-level donors or deep-levelacceptors, respectively. The acceptor contaminants and ionized acceptorcontaminants may be replaced with donor contaminants and ionized donorcontaminants that provide free electrons to the semiconductor. Thedeep-level dopants may then include deep-level acceptor states whichtrap the free electrons, thus reducing the concentration of freeelectrons in the semiconductor.

A first layer described and/or depicted herein as “on” or “over” asecond layer can be immediately adjacent to the second layer, or one ormore intervening layers can be between the first and second layers. Afirst layer that is described and/or depicted herein as “directly on” or“directly over” a second layer or a substrate is immediately adjacent tothe second layer or substrate with no intervening layer present, otherthan possibly an intervening alloy layer that may form due to mixing ofthe first layer with the second layer or substrate. In addition, a firstlayer that is described and/or depicted herein as being “on,” “over,”“directly on,” or “directly over” a second layer or substrate may coverthe entire second layer or substrate, or a portion of the second layeror substrate.

A substrate is placed on a substrate holder during layer growth, and soa top surface or an upper surface is the surface of the substrate orlayer furthest from the substrate holder, while a bottom surface or alower surface is the surface of the substrate or layer nearest to thesubstrate holder.

From the above description of the method it is manifest that varioustechniques may be used for implementing the concepts of the methodwithout departing from its scope. The described embodiments are to beconsidered in all respects as illustrative and not restrictive. Itshould also be understood that the method is not limited to theparticular examples described herein, but can be implemented in otherexamples without departing from the scope of the claims. Similarly,while operations are depicted in the drawings in a particular order,this should not be understood as requiring that such operations beperformed in the particular order shown or in sequential order, or thatall illustrated operations be performed, to achieve desirable results.

1. A semiconductor, comprising: a substrate; a nucleation layer over thesubstrate and having deep-level dopants; and a III-V layer formed overthe nucleation layer; wherein: at least one of the substrate and thenucleation layer include ionized contaminants, a concentration of thedeep-level dopants is at least as high as a concentration of the ionizedcontaminants, and a concentration of free holes in the substrate and inthe nucleation layer is less than 10¹⁶ cm⁻³.
 2. The semiconductor ofclaim 1, wherein: the substrate comprises a substrate material; and thedeep-level dopants comprise a deep-level dopant species havingdeep-level states being separated from conduction and valence bands ofthe substrate material by between 0.3 eV and 0.6 eV.
 3. Thesemiconductor of claim 1, further comprising a heterostructure betweenthe substrate and the nucleation layer.
 4. The semiconductor of claim 1,wherein the deep-level dopant comprises vanadium.
 5. The semiconductorof claim 1, wherein the deep-level dopant comprises iron.
 6. Thesemiconductor of claim 1, wherein the deep-level dopant comprisessulfur.
 7. The semiconductor of claim 1, wherein the ionizedcontaminants comprise a Group III species.
 8. The semiconductor of claim1, wherein the ionized contaminants comprise ionized acceptorcontaminants.
 9. The semiconductor of claim 1, wherein the concentrationof the deep-level dopants is between 10¹⁵ cm⁻³ and 10¹⁹ cm⁻³.
 10. Thesemiconductor of claim 1, wherein the concentration of the deep-leveldopants is between 10¹⁶ cm⁻³ and 10¹⁸ cm⁻³.
 11. (canceled)
 12. Thesemiconductor of claim 1, wherein a concentration of free holes in thesubstrate and in the nucleation layer is less than 10¹⁵ cm⁻³.
 13. Thesemiconductor of claim 1, wherein a thickness of the nucleation layer isbetween 1 nm and 100 nm.
 14. The semiconductor of claim 1, wherein athickness of the nucleation layer is between 10 nm and 1 μm.
 15. Thesemiconductor of claim 1, wherein a thickness of the nucleation layer isbetween 100 nm and 10 μm.
 16. The semiconductor of claim 1, wherein afirst concentration of the deep-level dopants at the surface of thenucleation layer nearest the substrate is higher than a secondconcentration of the deep-level dopants at the surface nearest the III-Vlayer.
 17. The semiconductor of claim 1, wherein the substrate materialis silicon.
 18. The semiconductor of claim 1, wherein the III-V layer isa III-nitride layer.
 19. A method of growing a semiconductor,comprising: growing a nucleation layer over a substrate, the nucleationlayer having deep-level dopants; and growing a III-V layer over thenucleation layer; wherein: at least one of the substrate and thenucleation layer include ionized contaminants, a concentration of thedeep-level dopants is at least as high as a concentration of the ionizedcontaminants, and a concentration of free holes in the substrate and inthe nucleation layer is less than 10¹⁶ cm⁻³.
 20. The method of claim 19,wherein: the substrate comprises a substrate material; and thedeep-level dopants comprise a deep-level dopant species havingdeep-level states being separated from the conduction and valence bandsof the substrate material by between 0.3 eV and 0.6 eV.
 21. The methodof claim 19, further comprising growing a heterostructure between thesubstrate and the nucleation layer.
 22. The method of claim 19, whereinthe deep-level dopants comprise vanadium.
 23. The method of claim 19,wherein the deep-level dopants comprise iron.
 24. The method of claim19, wherein the deep-level dopants comprise sulfur.
 25. The method ofclaim 19, wherein the ionized contaminants comprise a Group III species.26. The method of claim 19, wherein the ionized contaminants compriseionized acceptor contaminants.
 27. The method of claim 19, wherein theconcentration of deep-level dopants is between 10¹⁵ cm⁻³ and 10¹⁹ cm⁻³.28. The method of claim 19, wherein the concentration of deep-leveldopants is between 10¹⁶ cm⁻³ and 10¹⁸ cm⁻³.
 29. (canceled)
 30. Themethod of claim 19, wherein a concentration of free holes in thesubstrate and in the nucleation layer is less than 10¹⁵ cm⁻³.
 31. Themethod of claim 19, wherein a thickness of the nucleation layer isbetween 1 nm and 100 nm.
 32. The method of claim 19, wherein a thicknessof the nucleation layer is between 10 nm and 1 μm.
 33. The method ofclaim 19, wherein a thickness of the nucleation layer is between 100 nmand 10 μm.
 34. The method of claim 19, wherein a first concentration ofthe deep-level dopants at the surface of the nucleation layer nearestthe substrate is higher than a second concentration of the deep-leveldopants at the surface nearest the III-V layer.
 35. The method of claim19, wherein the substrate material is silicon.
 36. The method of claim19, wherein the III-V layer is a III-nitride layer.
 37. The method ofclaim 19, comprising growing the nucleation layer and III-V layer bymetalorganic chemical vapor deposition.
 38. The method of claim 19,comprising growing the nucleation layer and the III-V layer by molecularbeam epitaxy.
 39. The method of claim 19, comprising growing thenucleation layer and the III-V layer by halide vapor phase epitaxy. 40.The method of claim 19, comprising growing the nucleation layer and theIII-V layer by physical vapor deposition.
 41. The semiconductor of claim1, wherein: a topmost layer of the substrate is silicon, and thenucleation layer is silicon.
 42. The method of claim 19, wherein: atopmost layer of the substrate is silicon, and the nucleation layer issilicon.